The epigraphic stela of Montoro (Cordoba): the earliest monumental script in Iberia?

A remarkable stela from Montoro, southern Spain, is unique in its morphology, epigraphic traits and landscape context. A programme of chemical characterisation, digital imaging, and geo-lithological and epigraphic analyses were conducted to determine its age and significance, and the results were integrated with data from archaeological investigations of the surrounding area. This multi-faceted approach allowed the stela to be interpreted within the context of early interactions between literate Mediterranean societies of the Late Bronze Age and Iron Age and non-literate Iberian societies. A key outcome of this research is a wider understanding of the complex patterns in the use and perception of early scripts.

Mesoporous ZnS-SiO2 nanocomposite was synthesized with a facile process. At first a large pore volume (1.86 cm(3).g(-1)), moderate pore size (about 12.8 nm) and moderate surface area (586 m(2).g(-1)) mesoporous SiO2 was synthesized in an acidic PH using cationic surfactant. ZnS nanoparticles were infiltrated in the porosities of the synthesized SiO2, with a room temperature post grafting method. The synthesized particles have been characterized with transmission electron microscopy (TEM), x-ray diffraction (XRD), x-ray photoelectron spectroscopy (XPS), Brunauer-Emmett-Teller (BET), furrier transformation infrared spectroscopy (FTIR) and diffuse reflectance spectroscopy (DRS). Results confirm the mesoporous characteristics of ZnS-SiO2 nanocomposite with specific surface area as high as 248 m(2).g(-1), pore volume of 0.89 cm(3).g(-1) and average pore diameter of about 14.4 nm. Simultaneous adsorption-photocatalytic behavior of this hybrid mesoporous nanocomposite for degradation of methylene blue (MB) was investigated. The efficiency of this material was compared with that of mesoporous SiO2 and also lone ZnS nanoparticles. Results showed that by using ultraviolet irradiation, ZnS-SiO2 can degrade greater than 85% of MB only after 3 min. The case for lone ZnS is less than 5% after 30 min. Degradation mechanism of MB using ZnS-SiO2 and ultraviolet radiation was explained with simultaneous adsorption and photocatalytic phenomena. Ultraviolet irradiation can degrade adsorbed MB of mesoporous SiO2 which can prevent it from saturation.

Cobalt Carbide Identified as Catalytic Site for the Dehydrogenation of Ethanol to Acetaldehyde

Two cobalt catalysts, Co/SBA-15 and Co/SiO2, have been studied in steam reforming of ethanol (SRE). Besides the steam reforming products, ethoxide dehydrogenation to acetaldehyde is observed as one of the main reactions. Although by hydrogen treatment cobalt is reduced to the metallic state, under SRE conditions, a phase appears that has been identified as cobalt carbide and correlates with acetaldehyde production. These findings provide insights about the catalytic sites, for SRE, in cobalt catalysts. Comparison with previous results shows that these conclusions are not translatable to other cobalt catalysts, stressing the importance of the support on the catalytic behavior of cobalt.

Photonic Tuning of the Emission Color of Nanophosphor Films Processed at High Temperature

Photonics offers new possibilities to tailor the photoluminescence process in phosphor-converted light emitting diodes. Herein, it is demonstrated that the emission color of thin layers of rare-earth doped nanocrystals can be strongly modulated in tunable spectral ranges using optical resonators specifically designed to this end. GdVO4:Dy3+ nanoparticles of controlled size and shape are synthesized using a solvothermal method with which highly transparent nanophosphor thin films are prepared. This paper designs and fabricates optical multilayers, which are transparent in the UV and resonant at the frequencies where the Dy3+ ions emit, to prove that the color coordinates of this emitter can be tuned from green to blue or yellow with unprecedented precision. Key to the achievement herein reported is the careful analysis of the structural and optical properties of thin nanophosphor layers with the processing temperature in order to achieve efficient photoluminescence while preserving the transparency of the film. The results open a new path for fundamental and applied research in solid-state lighting in which photonic nanostructures allow controlling the emission properties of state-of-the-art materials without altering their structure or chemical composition.

We present herein an evolved methodology for the growth of nanocrystalline hierarchical nanotubes combining physical vapor deposition of organic nanowires (ONWs) and plasma enhanced chemical vacuum deposition of anatase TiO2 layers. The ONWs act as vacuum removable 1D and 3D templates, with the whole process occurring at temperatures ranging from RT to 250 degrees C. As a result, a high density of hierarchical nanotubes with tunable diameter, length and tailored wall microstructures are formed on a variety of processable substrates as metal and metal oxide films or nanoparticles including transparent conductive oxides. The reiteration of the process leads to the development of an unprecedented 3D nanoarchitecture formed by stacking the layers of hierarchical TiO2 nanotubes. As a proof of concept, we present the superior performance of the 3D nanoarchitecture as a photoanode within an excitonic solar cell with efficiencies as high as 4.69% for a nominal thickness of the anatase layer below 2.75 mu m. Mechanical stability and straightforward implementation in devices are demonstrated at the same time. The process is extendable to other functional oxides fabricated by plasma-assisted methods with readily available applications in energy harvesting and storage, catalysis and nanosensing.

This article establishes the bases for a vacuum and plasma supported methodology for the fabrication at mild temperatures of nanostructured platinum in the form of porous layers and nanocolumns using platinum octaethylporphyrin as precursor. In addition, the application of these materials as tunable optical filters and nano-counterelectrodes is proved. On one hand, the transparency in the ultraviolet-visible-near infrared range can be adjusted precisely between 70% and 1% by tuning the deposition and processing conditions, obtaining a high spectral planarity. Deviations of the spectra from an ideal flat filter are below 4%, paving the way to the fabrication of neutral density filters. The transparency limit values yield a sheet resistivity of approximate to 1350 and 120 Omega square(-1), respectively. On the other hand, the catalytic properties of the nanostructures are further demonstrated by their implementation as counterelectrodes of excitonic solar cells surpassing the performance of commercial platinum as counterelectrode in a 20% of the overall cell efficiency due to simultaneous enhancement of short-circuit photocurrent and open-circuit photovoltage. One of the most interesting features of the developed methodology is its straightforward application to other metal porphyrins and phthalocyanines readily sublimable under mild vacuum and temperature conditions.

M/WO3 (M = Pt, Pd) systems formed by a porous WO3 thin film decorated by metal nanoparticles are known for their reversible coloring upon exposure to H2 at room temperature. In this work, this gasochromic behavior is investigated in situ by means of near-ambient photoemission (NAPP). Pt/WO3 systems formed by very small Pt nanoparticles (10 ± 1 nm average size) incorporated in the pores of nanocolumnar WO3 thin films prepared by magnetron sputtering at an oblique angle have been exposed to a small pressure of hydrogen at ambient temperature. The recorded UV–vis transmission spectra showed the reversible appearance of a very intense absorption band responsible for the blue coloration of these gasochromic films. In an equivalent experiment carried out in the NAPP spectrometer, W 4f, O 1s, Pt 4f, and valence band photoemission spectra have been recorded at various photon energies to follow the evolution of the reduced tungsten species and hydroxyl groups formed upon film exposure to hydrogen. The obtained results are compared with those of a conventional X-ray photoemission study after hydrogen exposure between 298 and 573 K. As investigated by NAPP, the gasochromic behavior at 298 K is accounted for by a reaction scheme in which hydrogen atoms resulting from the dissociation of H2 onto the Pt nanoparticles are spilt over to the WO3 substrate where they form surface OH–/H2O species and subsurface W5+ cations preferentially located in buried layers of the oxide network.

Plasma treatment is recognized as a suitable technology to improve germination efficiency of numerous seeds. In this work Quinoa seeds have been subjected to air plasma treatments both at atmospheric and low pressure and improvements found in germination rate and percentage of success. Seed water uptake by exposure to water vapor, although slightly greater for plasma treated seeds, did not justify the observed germination improvement. To identify other possible factors contributing to germination, the chemical changes experienced by outer parts of the seed upon plasma exposure have been investigated by X-ray photoemission spectroscopy (XPS) and scanning electron microscopy (SEM-EDX). XPS revealed that the outer layers of the Quinoa plasma treated seeds were highly oxidized and appeared enriched in potassium ions and adsorbed nitrate species. Simultaneously, SEM-EDX showed that the enrichment in potassium and other mineral elements extended to the seed pericarp and closer zones. The disappearance from the surface of both potassium ions and nitrate species upon exposure of the plasma treated seeds to water vapor is proposed as a factor favoring germination. The use of XPS to study chemical changes at seed surfaces induced by plasma treatments is deemed very important to unravel the mechanisms contributing to germination improvement.

Characterization of of mechanosynthesized Bi1-xSmxFeO3 samples unencumbered by secondary phases or compositional inhomogeneity

High-quality samples, in terms of phase purity and dielectric properties, of composition Bi1-xSmxFeO3 (0.05 <= x <= 0.20) have for the first time been prepared by mechanosynthesis. Close inspection of the powder diffraction data, analysis via Rietveld refinement and TEM microscopy demonstrates that the Bi1-xSmxFeO3 samples contain only perovskite phases. Additionally, by a combination of Rietveld analysis, TEM, DSC, temperature-dependent XRD and permittivity data a tentative phase diagram has been proposed where the high temperature paraelectric phase Pnma has been confirmed for samarium substituted BiFeO3. Regarding the physical properties, the samples resulted to be electrically homogenous and highly insulating at room temperature, suggesting that other sources of conductivity, such as mixed valence of Fe associated with possible oxygen non-stoichiometry, have been avoided during the samples synthesis. In spite of the high quality of the samples, the dielectric and magnetic behaviour of the Bi1-xSmxFeO3 samples change only modestly on Sm substitution, with neither a great change in the resistivity or remnant magnetisation of Sm substituted samples in comparison with BiFeO3.

Cs+ immobilization by designed micaceous adsorbent under subcritical conditions

The adsorption of Cs+ by clay minerals is a complicate process, being cation exchange and frayed-edge sites the major mechanisms that govern it. However, environmental variables have a significant impact on the process. In this work, the influence of the temperature and time in the cesium adsorption capacity of Na-Mica-n (n = 2 and 4) have been explored under subcritical conditions. Those synthetic micas were able to immobilize cations Cs+ combining adsorption at nonspecific sites, at specific sites and chemical reaction. The distribution constant of Cs+ was larger in the Na-Mica-2 denoting a higher concentration of specific adsorption sites when layer charge decreased.

Moisture-induced degradation in perovskite solar cells was thoroughly investigated by structural (SEM, EDS, XRD and XPS) and device characterization (impedance and intensity modulated photocurrent spectroscopy) techniques. Both the influence of the perovskite composition and the nature of the hole selective material were analyzed. The degradation rate was found to be significantly slower for mixed perovskites and P3HT-based devices. However, for a fixed degradation degree (defined as a 50% drop from the initial photocurrent), all configurations show similar features in small-perturbation analysis. Thus, a new mid-frequency signal appears in the impedance response, which seems to be related to charge accumulation at the interfaces. In addition, faster recombination, with a more important surface contribution, and slower transport were clearly inferred from our results. Both features can be associated with the deterioration of the contacts and the formation of a higher number of grain boundaries.

The Oxy-CaL process: A novel CO2 capture system by integrating partial oxy-combustion with the Calcium-Looping process

This paper proposes a novel CO2 capture technology from the integration of partial oxy-combustion and the Calcium -Looping capture process based on the multicycle carbonation/calcination of limestone derived CaO. The concentration of CO2 in the carbonator reactor is increased by means of partial oxycombustion, which enhances the multicycle CaO conversion according to thermogravimetric analysis results carried out in our work, thus improving the CO2 capture efficiency. On the other hand, energy consumption for partial oxy-combustion is substantially reduced as compared to total oxy-combustion. All in all, process simulations indicate that the integration of both processes has potential advantages mainly regarding power plant flexibility whereas the overall energy penalty is not increased. Thus, the resulting energy consumption per kilogram of CO2 avoided is kept smaller than 4 MI/kg CO2, which remains below the typical values reported for total oxy-combustion and amine based CO2 capture systems whereas CO2 capture efficiency is enhanced in comparison with the Calcium -Looping process.

A novel, simple and rapid route to the synthesis of boron cabonitride nanosheets: combustive gaseous unfolding

The ternary compound boron carbonitride (BCN) was synthesized in the form of few-layer nanosheets through a mechanically induced self-sustaining reaction (MSR). Magnesium was used to reduce boron trioxide in the presence of melamine in a combustive manner. The process to form the nanostructured material was very rapid (less than 40 min). The prepared powder was investigated by various techniques such as X-ray diffraction (XRD), Fourier Transform infrared (FTIR), Micro-Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), high-resolution transmission electron microscopy (HRTEM), and electron energy loss spectroscopy (EELS). The thermal stability and the optical behavior of the BCN nanosheets were also studied by thermal analysis and UV-vis spectroscopy, respectively. The formation mechanism of the nanosheet morphology was described in detail.

One-dimensional (1D) nanostructured surfaces based on high-density arrays of nanowires and nanotubes of photoactive titanium dioxide (TiO2) present a tunable wetting behavior from superhydrophobic to superhydrophilic states. These situations are depicted in a reversible way by simply irradiating with ultraviolet light (superhydrophobic to superhydrophilic) and storage in dark. In this article, we combine in situ environmental scanning electron microscopy (ESEM) and near ambient pressure photoemission analysis (NAPP) to understand this transition. These experiments reveal complementary information at microscopic and atomic level reflecting the surface wettability and chemical state modifications experienced by these 1D surfaces upon irradiation. We pay special attention to the role of the water condensation mechanisms and try to elucidate the relationship between apparent water contact angles of sessile drops under ambient conditions at the macroscale with the formation of droplets by water condensation at low temperature and increasing humidity on the nanotubes surfaces. Thus, for the as-grown nanotubes, we reveal a metastable and superhydrophobic Cassie state for sessile drops that tunes toward water dropwise condensation at the microscale compatible with a partial hydrophobic Wenzel state. For the UV-irradiated surfaces, a filmwise wetting behavior is observed for both condensed water and sessile droplets. NAPP analyses show a hydroxyl accumulation on the as-grown nanotubes surfaces during the exposure to water condensation conditions, whereas the water filmwise condensation on a previously hydroxyl enriched surface is proved for the superhydrophilic counterpart.

Effect of the impact energy on the chemical homogeneity of a (Ti,Ta,Nb)(C,N) solid solution obtained via a mechanically induced self-sustaining reaction

A titanium-tantalum-niobium carbonitride solid solution, (Ti,Ta,Nb)(C,N), was synthesised in a planetary mill via a mechanochemical process that involves a mechanically induced self-sustaining reaction (MSR) from stoichiometric Ti/Ta/Nb/C mixtures that are milled under a nitrogen atmosphere. The influence of the spinning rate of the planetary mill, which determines the impact energy of the milling process, on the ignition time (t(ig)) of the MSR process as well as the chemical homogeneity of the final product was analysed. The results indicated that the dependence of tig on the spinning rate followed a potential function with a potential factor of 4.85, implying a remarkable reduction in the milling time required to induce the self-sustaining reaction at increasing spinning rates (i.e., from 4200 min at 200 rpm to 15 min at 800 rpm). However, the chemical and structural characterisation of the obtained products at ignition without any extra milling treatment indicated that a single solid solution phase was only obtained at the lowest spinning rates (i.e., less than 300 rpm). At increasing rates, the relative amount of the intended solid solution phase continuously decreased, and new undesirable secondary phases were formed. Despite the long milling times required for the milling experiments that were performed at the slowest spinning rates, iron contamination from the milling media was negligible due to the low intensity milling regime.

Alumina (Al2O3) ceramic composites reinforced with either graphene oxide (GO) or carbon nanofibers (CNFs) were prepared using Spark Plasma Sintering. The effects of GO and CNFs on the microstructure and in consequence on their mechanical properties were investigated. The microstructure of the sintered materials have been characterized quantitatively prior to and after the creep experiments in order to discover the deformation mechanism. Graphene-oxide reinforced alumina composites were found to be more creep resistant than carbon nanofibers-reinforced alumina ones or monolithic alumina with the same grain size distribution. In all the cases, grain boundary sliding was identified as the deformation mechanism

About the enhancement of chemical yield during the atmospheric plasma synthesis of ammonia in a ferroelectric packed bed reactor

Plasma reactions offer an attractive alternative route for the synthesis of a variety of valuable chemical compounds. Here we investigate the parameters that determine the efficiency of ammonia synthesis in a ferroelectric packed bed dielectric barrier discharge (DBD) reactor. The effects of varying the operating frequency, the size of the ferroelectric pellets and the inter-electrode distance have been systematically studied. Under optimised conditions nitrogen conversions in excess of 7% were achieved, higher than those previously obtained using DBD reactors. These findings are discussed with respect to variations in the electrical characteristics of the reactor under operating conditions and in the light of emission spectra obtained as a function of reactant flow rates. These encouraging results signpost future developments that could very substantially improve the efficiency of ammonia synthesis by means of DBD technology.

A compact and portable optofluidic device for detection of liquid properties and label-free sensing

Optofluidic lasers have been widely investigated over the last few years mainly because they can be easily integrated in sensor devices. However, high power pulse lasers arc required as excitation sources, which, in practice, limit the portability of the system. Trying to overcome some of these limitations, in this paper we propose the combined use of a small CW laser with a Fabry-Perot optofluidic planar microcavity showing high sensitivity and versatility for detection of liquid properties and label-free sensing. Firstly, a fluorescein solution in ethanol is used to demonstrate the high performances of the FP microcavity as a temperature sensor both in the laser (high pump power above laser threshold) and in the fluorescence (low pump power) regimes. A shift in the wavelength of the resonant cavity modes is used to detect changes in the temperature and our results show that high sensitivities could be already obtained using cheap and portable CW diode lasers. In the second part of the paper, the demonstration of this portable device for label-free sensing is illustrated under low CW pumping. The wavelength positions of the optolluidic resonant modes are used to detect glucose concentrations in water solutions using a protein labelled with a fluorescent dye as the active medium.

Failure mode and effect analysis of a large scale thin-film CIGS photovoltaic module

The efficiency of thin-film CIGS based cells at the laboratory scale is now getting closer to conventional Silicon technologies. As a consequence, the long-term stability of CIGS is now one of the main challenges left to address in order to assess its potential as an alternative for photovoltaic plants. This paper reports an overview of the critical risks for the commercial viability of the CIGS thin-film technology. The key causes of the potential failures of this technology are determined through the Failure Mode Analysis and Effects (FMEA) methodology. To validate the results obtained from the FMEA, aging tests and outdoor monitoring were also carried out. Based on the results obtained, we argue that the encapsulation material is the main cause of degradation in CIGS modules.

Non-isothermal Characterization of the Precipitation Hardening of a Cu-11Ni-19Zn-1Sn Alloy

The precipitation hardening of a Cu-11Ni-19Zn-1Sn alloy has been studied by means of Differential Scanning Calorimetry (DSC), High-Resolution Transmission Electron Microscopy (HRTEM), and hardness measurements. The calorimetric curves, in the range of temperatures analyzed, show the presence of one exothermic reaction followed by an endothermic one. The exothermic DSC peak is due to the segregation of Cu2NiZn precipitates and it is associated to a noticeable improvement of the mechanical properties of the alloy. The endothermic effect is associated to the dissolution of the Cu2NiZn precipitates into the copper matrix for restoring the starting Cu-11Ni-19Zn-1Sn homogeneous solid solution. The reaction mechanisms of these processes have been proposed from the kinetic analysis of the exothermic and endothermic DSC signals. The results obtained point out that tin plays a decisive role on the precipitation hardening of the alloy, because age hardening is not observed in the case of a Cu-Ni-Zn ternary alloy of similar composition.